*Goat Cheese Quality in North Macedonia DOI: http://dx.doi.org/10.5772/intechopen.84545*

**Figure 5.**

*Goats (Capra) - From Ancient to Modern*

**Parameters Cheeses Ripening time (days)**

Total GR 10.19 ± 0.95bA 8.43 ± 0.04aA 9.59 ± 0.79abA Protein GP 10.13 ± 0.94aA 9.90 ± 0.42aB 10.88 ± 0.20aB WSN-SN GR 7.74 ± 1.01aA 8.64 ± 0.37aB 7.31 ± 1.02aB (% of TN) GP 5.82 ± 0.37bA 6.22 ± 1.58bA 2.93 ± 0.37aB TCA-SN GR 2.44 ± 0.65aA 3.05 ± 0.02aB 2.92 ± 0.46aB (% of TN) GP 1.71 ± 0.24abA 2.39 ± 0.52bA 1.44 ± 0.21aA TFAA GR 0.41 ± 0.00eB 0.30 ± 0.01aA 0.44 ± 0.02dB mg Leu/g GP 0.35 ± 0.00cA 0.30 ± 0.00bA 0.39 ± 0.01dA *SD, standard deviation; TFAA, total free amino acid; DM, dry matter; WSN, water-soluble nitrogen. TN, total nitrogen; TCA, 12% trichloroacetic acid-soluble nitrogen. a, dMeans ± SD within a row and A–BMeans ± SD within a column with no common superscript capital letters differ (P < 0.05), respectively. Adapted from Sulejmani and Hayalogu [18]*

*Chemical parameters during ripening in raw (GR) and pasteurized (GP) white-brined goat cheeses.*

*Parameters* **Kumanovo Radovish** pH 5.01 ± 0.01 5.43 ± 0.05 % Lactic acid 1.73 ± 0.10 4.45 ± 0.13 Dry matter, % 68.43 ± 0.11 57.34 ± 0.21 Moisture, % 31.57 ± 0.11 42.67 ± 0.21 Fat, % 29.63 ± 0.25 26.00 ± 0.41 Fat(dm), % 43.29 ± 0.35 45.35 ± 0.84 Salt, % 4.11 ± 0.07 8.18 ± 0.38 Proteins, % 32.81 ± 1.09 21.32 ± 0.69

**1 60 120**

**120**

**Table 2.**

TN(g100 g<sup>−</sup><sup>1</sup>

**Table 3.**

*Adapted from Sulejmani et al. [31]*

that had pasteurization [30].

At the beginning the ripening of white-brined goat cheese, as1-CN (f24–199) and c2-casein were produced, indicating high activity of chymosin and plasmin. However, it can be seen that b-casein reduction rate was smaller than as1-casein that of during ripening (**Figure 5**). After 60 days of ripening in the GR cheeses, the band corresponding to as1-I-casein (as1-CN f102–191) was present in all electrophoretograms of the samples, as a result of hydrolysis of as1- casein. A reduction of as1- and b-casein was obviously faster in the GR cheeses than in the GP cheeses, probably due to the native microorganisms and indigenous milk enzymes. Significantly inactivated indigenous and milk proteinases indicates on great impact

*Physical-chemical parameters of mixed goat/ewes milk cheese from different geographical locations.*

cheese) 5.15 ± 0.17 3.34 ± 0.11

WSN (% TN) 10.34 ± 1.06 32.76 ± 0.95 TCA-N (% TN) 6.37 ± 0.70 4.60 ± 0.04 TFAA(mgLeu/g) 3.18 ± 0.56 3.72 ± 0.13

As it is obviously shown in **Figure 5**, the hydrolysis of as1-casein was faster in the GR cheeses during ripening obviously as a result of the higher activity of

*(Left) Urea-PAGE of the water-insoluble fractions of white goat milk cheeses made using raw (GR) or pasteurized (GP) method during 120 days of ripening (right) (with permission from John Wiley and Sons) [10].*

indigenous proteinases in the curd, which is exactly associated with the heat degree of the milk heat.

Some differences were observed during ripening for the fractions of peptides, which were eluted in the GR cheeses at higher quantity at the end of ripening than the beginning of ripening. Common peaks were evident in the 30 and 60 days of ripening in all of the chromatograms, with an increase in concentration of peptides during ripening, which were mainly eluted between the 56th and 76th min. In the chromatogram, between 64 and 74 min, the peak heights in the cheeses were generally much higher than in other cheese samples until the 120th day of ripening (**Figure 6**).

The analysis of free amino acids in white-brined goat cheese confirmed the presence of all amino acids except tyrosine (**Table 4**). The quantity of free amino acids is low because of particular process of fermentation. Due to the high concentration of salt and low ripening temperature of white brine, the participation of thermophilic lactic acid bacteria in ripening is minimal, and this cheese is defined by a weaker breakdown of paracasein.

The volatile components of white-brined goat cheeses have not previously been studied. They consisted of 12 acids, 14 esters, 6 ketones, 3 alcohols, 4 terpenes, and 6 miscellaneous compounds (**Table 2**). Acids, alcohols, and ketones constituted the principal chemical groups during ripening (mean volatile concentration of 51, 16, and 12% w/w of total compounds, respectively). The raw goat milk (GR) cheeses were by a higher quantity (78%) of total volatile compounds than the pasteurized goat milk (GP) cheeses, during ripening. Compared with day 1, a significant decrease in the total quantity of volatile compounds (except ketones and alcohols) was found after 120 days of ripening. Carboxylic acids are the principal volatile

### **Figure 6.**

*Reverse-phase HPLC profiles of the water-soluble fraction of white goat milk cheeses made using raw milk during 120 days of ripening [10].*


**123**

*Goat Cheese Quality in North Macedonia DOI: http://dx.doi.org/10.5772/intechopen.84545*

GP cheeses (14%).

ture of the cheeses.

Macedonian white goat cheeses.

their concentration were 13773.8 μg 100 g<sup>−</sup><sup>1</sup>

ated with pH and salt content [35].

class in Macedonian white goat cheese (with 51% of total volatile compounds). The raw goat milk (GR) cheeses were characterized by higher quantity (86%) of total acids than the pasteurized goat milk (GP) cheeses during ripening. Milk heat treatment significantly (*P <* 0.05) influenced the concentrations of two volatile fatty acids (hexanoic acid and octanoic acid) (**Table 2**). Similarly, these compounds have been shown to be the principal volatile class in other goat milk cheeses [32]. The main acid was hexanoic acid (40% of total acids), and this was identified at significantly higher quantity in GR cheeses at 60 days of ripening. 3-Methylbutanoic acid was the most abundant branched chain fatty acid found in Macedonian goat cheese. This is in agreement with the findings of Beuvier et al. [33]. During ripening, total acids were at a higher concentration in the GR cheeses (86%) in comparison with

Caproic acid is a product of lipolysis, which significantly contributes to the smell of goat cheese [33]. Karagul et al. [34] explored the level of proteolysis in "Ezine" cheese, produced from a mixture of goat milk(40%), sheep's milk (45–55%), and cow's milk (up to 15%) without starter culture, during 8 months ripening. Urea-PAGE assay confirmed that αs-casein decomposes very quickly, while the β-casein degradations are almost constant. Differences in the rate of degradation are associ-

Flavor is the main properties that influence the selection and consumption of cheeses. The effect of fatty acids on the sensory properties of different types of goat milk cheese is essential. The concentration of butyric acid is increased during the ripening of cheeses mainly higher of 50% from the total concentration in the beginning of its production (mozarella 66.35%, white-brined 74.58%, and pecorino 51.28%) [9]. The reason for the lower degree of formation of butyric acid during ripening and especially at the end of ripening of the cheeses is assumed to be the lack of a free substrate for conversion into fatty acids by way of lipolysis or reduction of enzyme activity due to the change in the microstruc-

At the first day of ripening in the raw goat milk cheeses (GR), acetic acid was identified at a higher concentration. Alcohols are the second most significant volatiles (16%) isolated in Macedonian goat cheese. At the end of ripening, the concentration of alcohols decreased to 40%, while after 60 days of ripening their quantity was 50%. The total esters were at higher quantity (98%) in raw goat milk (GR) cheeses than pasteurized goat milk (GP) cheeses during ripening. At the 60th day of ripening, a very high quantity of 3-methyl-1-butanol was found in the GR cheeses (**Table 5**). Heat treatment of the curd did not affect branched alcohols (except 2-ethyl-1-hexanol). 2-Propanone and 2-heptanone were the most abundant ketones among total of six ketones representing 54% and 13% of the total quantity of ketones, respectively. Higher quantity (77%) of total esters was characterized in the raw goat milk (GR) cheeses rather than the pasteurized goat milk (GP) cheeses during ripening. Because of particular odors and low perception thresholds, ester is very significant compounds in dairy products [36]. 2-Propanone and 2-heptanone were predominant ketones among six ketones that were identified in the

Five different acids that were identified in the Goat beaten cheese from

ferent acids were identified in the goat beaten cheese from the Radoviš region, and

and decanoic acids were responsible for the characteristic aroma of goat cheeses, and their contribution to the volatile profile of beaten cheeses has been shown in this study as well, giving rise to the trivial terms caproic, caprylic, and capric acids, respectively. In addition 2-heptanone was identified at highest concentration in

were reported. Six dif-

, respectively [31]. Hexanoic, octanoic,

Kumanovo region with concentration of 13347.2 μg 100 g<sup>−</sup><sup>1</sup>

### **Table 4.**

*Free amino acid concentration in white-brined goat cheese.*

### *Goat Cheese Quality in North Macedonia DOI: http://dx.doi.org/10.5772/intechopen.84545*

*Goats (Capra) - From Ancient to Modern*

**Free amino acids mg % Ripening**

Lysine 16.2 ± 0.31 33.11 ± 0.41 Histidine 2.2 ± 0.13 16.12 ± 0.71 Arginin 2.7 ± 0.71 4.85 ± 0.27 Threonine 2.60 ± 0.78 3.71 ± 0.62 Valin 11.78 ± 0.61 14.80 ± 0.16 Metionin 6.11 ± 0.43 8.71 ± 0.62 Isoleucin 3.21 ± 0.62 4.52 ± 0.27 Leucine 11.72 ± 0.31 21.57 ± 0.36 Phenylalanine 4.11 ± 0.62 15.61 ± 0.31 *Total essential amino acids* **60.63 ± 0.64 123.01 ± 0.74** Asparagin acid 3.8 ± 0.11 9.11 ± 0.37 Serin 6.10 ± 0.18 12.11 ± 0.38 Glutamic acid 6.70 ± 0.79 9.28 ± 0.65 Proline 1.50 ± 0.28 3.61 ± 0.33 Glycine — 6.63 ± 0.58 Alanin 3.31 ± 0.41 4.11 ± 0.43 Cistin 4.81 ± 0.11 7.51 ± 0.38 Tirozin — — *Total nonessential amino acid* **26.22 ± 0.53 52.36 ± 0.59** *Total quantity* **89.18 ± 0.58 176.32 ± 0.71**

*Reverse-phase HPLC profiles of the water-soluble fraction of white goat milk cheeses made using raw milk* 

**Day 15 Day 60**

**122**

**Table 4.**

**Figure 6.**

*during 120 days of ripening [10].*

*Adapted from Srbinovska [16]*

*Free amino acid concentration in white-brined goat cheese.*

class in Macedonian white goat cheese (with 51% of total volatile compounds). The raw goat milk (GR) cheeses were characterized by higher quantity (86%) of total acids than the pasteurized goat milk (GP) cheeses during ripening. Milk heat treatment significantly (*P <* 0.05) influenced the concentrations of two volatile fatty acids (hexanoic acid and octanoic acid) (**Table 2**). Similarly, these compounds have been shown to be the principal volatile class in other goat milk cheeses [32]. The main acid was hexanoic acid (40% of total acids), and this was identified at significantly higher quantity in GR cheeses at 60 days of ripening. 3-Methylbutanoic acid was the most abundant branched chain fatty acid found in Macedonian goat cheese. This is in agreement with the findings of Beuvier et al. [33]. During ripening, total acids were at a higher concentration in the GR cheeses (86%) in comparison with GP cheeses (14%).

Caproic acid is a product of lipolysis, which significantly contributes to the smell of goat cheese [33]. Karagul et al. [34] explored the level of proteolysis in "Ezine" cheese, produced from a mixture of goat milk(40%), sheep's milk (45–55%), and cow's milk (up to 15%) without starter culture, during 8 months ripening. Urea-PAGE assay confirmed that αs-casein decomposes very quickly, while the β-casein degradations are almost constant. Differences in the rate of degradation are associated with pH and salt content [35].

Flavor is the main properties that influence the selection and consumption of cheeses. The effect of fatty acids on the sensory properties of different types of goat milk cheese is essential. The concentration of butyric acid is increased during the ripening of cheeses mainly higher of 50% from the total concentration in the beginning of its production (mozarella 66.35%, white-brined 74.58%, and pecorino 51.28%) [9]. The reason for the lower degree of formation of butyric acid during ripening and especially at the end of ripening of the cheeses is assumed to be the lack of a free substrate for conversion into fatty acids by way of lipolysis or reduction of enzyme activity due to the change in the microstructure of the cheeses.

At the first day of ripening in the raw goat milk cheeses (GR), acetic acid was identified at a higher concentration. Alcohols are the second most significant volatiles (16%) isolated in Macedonian goat cheese. At the end of ripening, the concentration of alcohols decreased to 40%, while after 60 days of ripening their quantity was 50%. The total esters were at higher quantity (98%) in raw goat milk (GR) cheeses than pasteurized goat milk (GP) cheeses during ripening. At the 60th day of ripening, a very high quantity of 3-methyl-1-butanol was found in the GR cheeses (**Table 5**). Heat treatment of the curd did not affect branched alcohols (except 2-ethyl-1-hexanol). 2-Propanone and 2-heptanone were the most abundant ketones among total of six ketones representing 54% and 13% of the total quantity of ketones, respectively. Higher quantity (77%) of total esters was characterized in the raw goat milk (GR) cheeses rather than the pasteurized goat milk (GP) cheeses during ripening. Because of particular odors and low perception thresholds, ester is very significant compounds in dairy products [36]. 2-Propanone and 2-heptanone were predominant ketones among six ketones that were identified in the Macedonian white goat cheeses.

Five different acids that were identified in the Goat beaten cheese from Kumanovo region with concentration of 13347.2 μg 100 g<sup>−</sup><sup>1</sup> were reported. Six different acids were identified in the goat beaten cheese from the Radoviš region, and their concentration were 13773.8 μg 100 g<sup>−</sup><sup>1</sup> , respectively [31]. Hexanoic, octanoic, and decanoic acids were responsible for the characteristic aroma of goat cheeses, and their contribution to the volatile profile of beaten cheeses has been shown in this study as well, giving rise to the trivial terms caproic, caprylic, and capric acids, respectively. In addition 2-heptanone was identified at highest concentration in


**125**

**Compounds**

*Total* *Esters* Methyl acetate

Ethyl acetate Methyl propanoate

Methyl butyrate

Methyl carbonate

Ethyl butyrate n-Butyl acetate Isoamyl acetate

Methyl caproate

Ethyl heptanoate

Isoamyl acetoacetate

Ethyl n-caproate

Dimethyl phthalate

Diethyl phthalate

*Total* *Terpenes*

dl-Limonene Cymene <para->

Alph.-thujene

15,942 18,287 14,771

54.96 ± 7.07

1.80 ± 2.54 0.10 ± 0.14

ND ND ND

109.79 ± 31.99

ND ND

ND ND ND

NS

NS

\*

6521 7447 7823 9645 9785 11,035 12,024 13,535 15,544 15,973 16,141 17,021 24,779 45,468

3.35 ± 1.90 19.43 ± 14.40

1.86 ± 0.86 2.28 ± 0.69 0.15 ± 0.21 1.65 ± 2.34 1.04 ± 1.47 1.59 ± 2.24 0.34 ± 0.49

ND 0.72 ± 1.02 0.17 ± 0.25 1.74 ± 2.46 1.77 ± 1.18 *36.10 ± 29.51*

9.12 ± 1.90 2.14 ± 3.03 4.56 ± 0.58 12.98 ± 5.42

2.70 ± 0.18

ND ND ND 2.56 ± 3.63 23.29 ± 32.93

ND ND 3.16 ± 4.47 25.06 ± 26.41 *85.58 ± 78.56*

3.17 ± 1.58 2.24 ± 1.88 2.30 ± 1.69 3.69 ± 4.12

ND ND ND ND ND ND ND ND ND 1.25 ± 1.77 *12.65 ± 11.04*

6.51 ± 1.12 6.18 ± 6.79 3.71 ± 0.21 14.19 ± 6.39

ND ND ND ND ND ND ND ND ND 1.11 ± 1.56 *31.70 ± 16.07*

NS NS NS NS

NS

NS

NS

NS

NS

NS

NS NS

\*

**RI**

**Day 1**

> **GP**

*25.12 ± 12.3*

**GR** *79.15 ± 55.8*

**GP** *24.3 ± 13.3*

**GR** *92.5 ± 55.9*

*Type*

**Day 60**

*P (type)*

*Goat Cheese Quality in North Macedonia DOI: http://dx.doi.org/10.5772/intechopen.84545*

> \*

*Goats (Capra) - From Ancient to Modern*

